Patent GB-974993-A (GB)
Title: Catalysts prepared from titanium-iodine compounds
IPC: C08F136/06
Filed: 1963-08-16
Abstract: Titanium alkoxy triiodides of the formula Ti(OR)I3 where R is an alkyl, alkoxyalkyl, aliphatic acyl, cycloalkyl or aralkyl radical having up to 20 carbon atoms may be prepared by reacting titanium tetraiodide with the corresponding monohydric alcohol in the molar ratio 1:1 and in the solid state. The reaction is preferably carried out in anhydrous aliphatic or aromatic solvents which do not contain any mobile hydrogen atoms, particularly in hydrocarbons. The reaction mixture may be heated to temperatures of at the most 180 DEG C. until the reaction is complete and the hydrogen iodide formed has escaped, the heating towards the end of the reaction may be carried out at reduced pressure and the titanium alkoxy triiodide obtained by evaporating the solvent. Polyhydric alcohols may be used instead of the monohydric alcohols. Furthermore carboxylic acids or vinyl carboxylic acids such as b -dicarbonyl compounds may be used instead of alcohols to produce analogous compounds.  Alternatively the titanium alkoxy triiodides may be prepared by co-proportionating titanium tetraiodide with a titanic acid ester by heating the compounds as solids or preferably in solution, to temperatures of at the most 180 DEG C. In the examples: (1) Titanium dodecylate triiodide is prepared from titanium tetraiodide and dodecyl alcohol; (2) The following titanium alkoxy triiodes and two reaction products with fatty acids are prepared from titanium tetraiodide: (n-C8H17O)TiI3; (i-C8H17O)TiI3 (n-C4H9O)TiI3; (C2H5O)TiI3; (CH3O)TiI3; (C4H9OCH2CH2O)TiI3; <PICT:0974993/C1/1> -O-TiI3; (CH3(CH2)7CH=CH(CH2)7COO)TiI3\t and (C17H35COO)TiI3; (3) Butoxy titanium triiodide is prepared by reacting titanium tetraiodide suspended in anhydrous benzene with titanium tetrabutylate. Specification 848,065 is referred to.ALSO:A hydrocarbon soluble catalyst composition suitable for polymerizing 1,3-butadiene comprises (a) an organoaluminium compound Al R1R11R111 in which R1, R11 and R111, which may be the same or different, are aliphatic or cycloaliphatic radicals having up to 20 carbon atoms and in addition R1 and R11 may be hydrogen atoms and (b) a titanium alkoxy triiodide Ti(OR)I3 where R is an alkyl, alkoxyalkyl, aliphatic acyl, cycloalkyl or aralkyl radical having up to 20 carbon atoms, the molar ratio of the aluminium in compound (a) to the titanium in compound (b) being in the range 2:1 to 20:1. Titanium tetrachloride or titanium tetrabromide may be used instead of a part of the titanium alkoxy triiodide, there being 0.01 to 4 mols of titanium tetrachloride or tetrabromide per mol of titanium alkoxy triiodide. Lists of catalyst components (a) and (b) are given. The activity of the catalysts can be altered by adding a -olefines such as isobutylene, vinyl cyclohexene, diisobutylene, (2,4,4-trimethylpentene-1) or styrene, or hydrocarbon halides such as isopropyl chloride, isopropyliodide, isopropylbromide, n-butyl chloride, dodecyliodide, iodoform, chloroform, cyclohexyl chloride or benzyl iodide in quantities of 0.5 to 20 mols per mol of titanium alkoxy triiodide after the reaction of titanium alkoxy triiodide with the organic aluminium compound. The catalyst composition is prepared at temperature from -10 DEG  to 50 DEG C. in the absence of air and moisture and in an aliphatic or aromatic hydrocarbon.  In the numerous examples butadiene is polymerized to a polymer having more than 80% of cis 1,4-linkages, the polymerization being stopped by adding a phenolic stabilizer and ethanolamine in a small amount of methanol or by adding 2,5-ditertbutyl-p-methylphenol and resinic acid, in both cases the polymer is then worked up with methanol. Specification 848,065 is referred to.